The kinetics of oxidation of 1-butene to methylethylketone in the presence of a homogeneous catalyst (complex of palladium + Mo-V-P heteropoly acid)

Chemical Engineering Journal, Volume 230,  2013, Pages 308-313.

E.G. Zhizhina, V.F. Odyakov.

 

Boreskov Institute of Catalysis, SB RAS, pr. Akad. Lavrentieva, 5, 630090 Novosibirsk, Russia

 

Abstract

The kinetics of the direct oxidation of 1-butene to methylethylketone (MEK) is studied in the presence of the new homogeneous catalyst namely an aqueous solution of a Pd salt and Mo-V-P heteropoly acid having non-Keggin-type composition Н₁₂P₃Mo₁₈V₇O₈₅ (HPA-7′). The catalyst (Pd + HPA-7′) is characterized by an increased stability and high selectivity (>97%) in the MEK production. The process (1) is realized in two stages: (2) + (3). In stage (2), 1-butene reacts with the catalyst in a butylene reactor 1 with the formation of MEK and a reduced form of the catalyst. After stripping of the product, the reduced catalyst is oxidized by air in a reactor 2 under increased pressure (stage 3). The experimental data allowed us to obtain the kinetic equation for the reaction rate of 1-butene oxidation used for the calculation of the tubular plug-flow reactor 1.

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Additional Information

The MEK process was realized in a pilot scale. Calculated power of the pilot plant was 250 kg MEK per day. The main devices of the plant were a butene reactor 1, a stripping column, and an air reactor 2. All parts of the pilot were filled with 1350 liters of solution of the (Pd + HPA-7’) catalyst, which was moving in a closed cycle. At the first step, the catalyst was reacted with liquid n‑butene in a tubular plug-flow reactor 1 at 60 °C, oxidizing n‑butene to MEK. Next the reduced (Pd + H_mHPA‑7’) catalyst with the product moved to the stripping column for MEK distillation. Then the reduced catalyst moved to a perfect-mixing air reactor 2 where it was oxidized by air oxygen at 160–170 °C and PO₂ = 4 bar. The regenerated catalyst moved again to the butene reactor 1 for the next cycle. Though the MEK process is two-stage, it is important that the MEK removal in the pilot plant occurs continuously. Pilot tests have showed that the MEK technology is promising for practical implementation.